Our invention relates to compounds defined according to the generic structure: ##STR3## processes for producing same, intermediates useful in said processes and uses thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles and colognes (wherein R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 each represents the same or different methyl or hydrogen with the provisos that:
(i) the sum total of the carbon atoms of R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 is three; PA1 (ii) when R.sub.7 is methyl, then R.sub.5 and R.sub.6 are each methyl and PA1 (iii) when R.sub.7 is hydrogen, then R.sub.3 or R.sub.4 is methyl. PA1 (i) the sum total of carbon atoms in R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 is three; PA1 (ii) when R.sub.7 is methyl, then R.sub.5 and R.sub.6 are both methyl, and PA1 (iii) when either R.sub.3 or R.sub.4 is methyl, then R.sub.7 is hydrogen and wherein R.sub.8 represents hydrogen, acetyl, alkoxyacyl, hydroxyacyl, or alkali metal carboxylate; and R.sub.9 is hydrogen or allyl with the additional proviso that R.sub.8 and R.sub.9 are not both hydrogen, or the subgenus having the structure: ##STR7## for use in augmenting or enhancing the aroma of perfume compositions, perfumed articles and colognes or the subgenera defined according to the structure: ##STR8## wherein Y is hydrogen or allyl and wherein Z represents methyl, alkoxy or alkali metal oxy or hydroxy useful as intermediates in preparing the compounds defined according to the structure: ##STR9## PA1 (i)--Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3, 1975, p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in Sulfuric Acid and Sulfuric-Phosphoric Acid Mixtures). PA1 (ii)--Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p. 281 (Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-Hexene and 3,5,5-Trimethyl-2-Heptene in Relation to the Dimerization of Isoamylenes). PA1 (iii)--Whitmore & Stahly, Vol. 67, J. Am. Chem. Soc., December, 1945, p. 2158 (Title: The Polymerization of Olefins. VIII The Depolymerization of Olefins in Relation to Intramolecular Rearrangements. II). PA1 (iv)--U.S. Pat. No. 3,627,700, issued on Dec. 14, 1971, (Zuech). PA1 (v)--U.S. Pat. No. 3,538,181, issued on Nov. 3, 1970, (Banks). PA1 (vi)--U.S. Pat. No. 3,461,184 issued on Aug. 12, 1969 (Hay, et al). PA1 (vii)--Gurwitsch, Chemische Berichte, 1912, Vol. 2, p. 796 (Production of Di-isoamylene From Isoamylene Using Mercury Acetate Catalyst).
Chemical compounds which can provide galbanum-like, fruity, pineapple-like, woody, ionone-like, bark-like, green, and oily-sweet aromas with floral undertones are highly desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions and perfumed articles are high in cost, unobtainable at times, vary in quality from one batch to another and/or are generally subject to variations in natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace, enhance, or augment the fragrance notes provided by natural essential oils or compositions thereof. Unfortunately many of the synthetic materials which can provide such nuances either have the desired nuances only to a relatively small degree or they contribute undesirable or unwanted odor to the compositions.
U.S. Pat. No. 4,346,237 issued on Aug. 24, 1982 (incorporated by reference herein) discloses the production of unsaturated branched ketones according to the reaction: ##STR4## wherein in each of the structures containing dashed lines, the structures represent mixtures of molecules wherein in each of the molecules, one of the dashed lines represents a carbon-carbon double bond and each of the other of the dashed lines represents a carbon-carbon single bond. These compounds so produced are indicated to be useful for their organoleptic properties in augmenting or enhancing the aroma or taste of consumable materials including perfume compositions, colognes and perfumed articles. It is noteworthy that the compounds defined according to the structure: ##STR5## have unsaturation in the structure and, in addition, have unsaturation at the "3" or "4" position in the structure and have the location of the "keto" group at the "2" position; and, in addition, contain 12 carbon atoms.
Nothing in the prior art discloses the compounds defined according to the genus: ##STR6## wherein R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 represent hydrogen or methyl with the provisos that:
The compounds of our invention defined according to the structure: ##STR10## are prepared using as a precursor the compounds defined according to the generic structure: ##STR11## the preparation of which is disclosed in application for United States Letters Patent Ser. No. 345,665 filed on Feb. 4, 1982, now U.S. Pat. No. 4,399,062, the disclosure of which is incorporated by reference herein. These compounds, in turn, are prepared using as an original precursor, "diisoamylene".
"Diisoamylene" is indicated to be synthesized in the following references:
United Kingdom Pat. No. 796,130 published on June 4, 1958 discloses the synthesis of polyalkylindanes by means of, interalia, reacting alpha-methylstyrene with trimethylethene (2-methyl-butene-2) in the presence of an acid catalyst such as sulfuric acid or boron trifluoride methyletherate. It is further indicated that such compounds are useful intermediates in the production of perfumery compounds. Apparently, however, the more volatile diisoamylenes produced as side-products in the reaction of 2-methyl-butene-2 with alpha-methylstyrene are discarded.
The diisoamylene useful as a starting material in the instant case may be distilled from the reaction product (as see Example A infra) at a temperature in the range of 36.degree.-40.degree. C.; a liquid temperature in the range of 74.degree.-94.degree. C. and a pressure of 4-5 mm/Hg.